Treatment of hydrocarbon oil



Dec. 5, 1933. v R 5 DAY 1,937,873

TREATMENT OF HYDROCARBON OIL Filed Feb. 11, 193? FRACTIONATOR 52 5| 4 ACCUMULATOR INVENTOR ROLAND 5. DAY

mw gg z Patented Dec. 5, 1933 HATENT OFFICE,

TREATMENT ,HYDROGARBON OIL Roland B. Day, Chicago, Illdassignor to Universal Oil Products Company tion of South Dakota:

Chicago, 111., a corpora- A plication Februaryll, 193,2. Serial No. 592,210.

6 Claims. (Cl. 19%36) This invention refers more particularly to the treatment ofcracked hydrocarbon distillates of approximate -motor -fuel boiling range though straight run distillates. of similar character and Jof higher boiling-range than gasoline may alsobentreatedm Cracked :distillates sometime contain large amounts of gum-forming constituents such as the diand tri olefins and sulfur compounds which in lflji bluderepresentatives of various groups such as mercaptans, thioethers, thiophenes, etcetera, along'with considerable percentages of hydrogen sulfldel a i In a more, specific sense the invention has ref.-\

?; Jerenceto a process-f or the treatment of hydrocar-- bona oil rvapors' whereby the distillates produced bytheir subsequentfractionation may be so -re fined and stabilized that further: chemical treat ment may notnbe nec'essaryto fit them for conal ZQtcsumption; rand: if .any further treatment necesv saryygitis \only of a minorcharacterm Thewpresent'w-inventionis directed to the treat- Y ment :ofocracked" hydrocarbon oil vapors for the removal of ngthe gum-forming ;:and sulfur comipoundsxmentioned andpossessesthe advanta e of ready] applicability, easeeof operation and :low

costs: i

a In :one-:specifickembodiment itheinvention com-v prises: "treating hydrocarbon oils,- particularly icracked hydrocarbonoil 1 distillates,- while rill. heat-= ed:waponoustcondition with hydrochloric acid"; and/or other halogen acids while i in contact with metallic catalysts, the catalysts having been-previously: activated or preconditioned before use in 3l1niithe aprocess-bytreatment with hydrochloric acid. Thencexact nature and-features of :the process mayqhe conveniently described-with reference to a icharacteristic Y 1 operation, andthis description: 5 WiHcbewgiven; in cconnection with the attached :drawing which shows diagrammatically in side elevationwa :plant layout in v(which theoperations V max: beiconducted though the particular appara tus shown is:only illustrative ofmany othersfrom which it ,difiers onlyginiminordetails. l

Referring to .the drawing, the, apparatus will, bseen to. consist of a treater 7 in whichthe solid contact materials may be disposed. inthe best manner. for affording intimate contact of the mixture] of halogen acid and oil vaporstherewith, a -fractionator2'l-for final rectification of the treated vaporsand the usual condensing and collectingequipment. v

oil vapors to be treated maybe admitted to thesystem through'a lineal, containing a control: valve 2, walve =2 1permittingarreducti0n orqrcrelease permitting either type of flow. treatments are to be conducted, the entering vahalogen-acids are considered, the description will of pressure if it betfound advantageous to employ lower pressures than those under which the vapors havebeen generated. Since either upward or downward flow of the vaporsand acid over the qsolidcontact materials may be employed, treater '7 is shown provided with the necessarylines for- When downfiow pors'may be passed through a line 3 containing a control valve 4 to upper vapor space 9 above the bed of contact material 8, and when upflow treatments are more suitable for any reason, the vapors-may be diverted through line 5, containingjncontrol valve 6, and enter lower vapor, space 10 below the perforated supportS'. The halogen acid employed may also be admitted to either the upper or lower vapor spaces of the treater, and sincethis acid will be hydrochloric in the majoriity ofcases unless minor amounts of the other be'confinedto the use of this acid. To provide for its-admission to the system, a line 13, con- -.,taining9a control valve; 14,, is shown, this line bran'ohinginto line 15, containing control valve 16 and terminating in distributing means 16 and line- 17,lcontainingcontrol valve 18, and terminati-ngin distributing means 18. The acid may beintroducedas-the anhydrous gas or as a solutiontof varying concentration, though in up fiow treatmentsit may at times be preferable to utilize the gas instead-of thesolution for reasons of distributionmln either event the'mixture of hydrocarbonoilwapors and hydrochloric acid in proper amountis introduced to the treater and caused toiflow upwardly or downwardly over. the contact materialsa The-pre-conditionihg of the contactmaterial inpthetreater may be ,eifected in several ways. For, example, the mass ,may be treated by allowingconcentrated hydrochloric acid to percolate. through it until the desired degree of chloride, formation is accomplished or the metals may be chlorinated by contact with hydrochloric acid vapor generated conveniently by heating concentrated;hydrochlorictacidiin the bottom of the towem Also thenecessary amount of acid may belintroduced as a substantially anhydrous gas or (mixed with -a certain amount of water vapor; the gasl or vapor mixture'having been generated in a small still of some sort, exterior to the treating-plant shown in the drawing. 7

In addition-to theme of hydrochloric acid for preconditioning contact masses, it may also be employed toregenerate their activity at a time whenrtheiriscatalytic effect has reached a low regulated to produce the desired results.

value on account of gradual contamination by carbonaceous depositions, the formation of sulfur compounds and the disintegration of composite masses. The general effect of the hydrochloric acid used in such cases will be equivalent to a washing to remove the contaminating substances and expose fresh metallic and chloride surfaces, the limits of such a treatment being fixed only by the fact that the more soluble metallic chlorides in the mixture will be gradually removed until the mass no longer contains metals in the desired proportions.

The contact materials may be employed in space 8 of treater 7 as a substantially uniform mass of proper sized particles to afford contact without unnecessary resistance to flow or they may be employed in layers of alternating or progressively varying composition or supported upon regularly spaced trays. When downflow treatments are conducted a certain amount of condensation may occur, although this may be prevented if found desirable by preliminary superheating of the vapors or by heating the treater to prevent drop in temperature. When upfiow treatments are conducted, a certain amount of fractionation may occur if no special precautions are taken to prevent condensation. In any event the conditions of operation in the treater will be The treater is shown provided with manheads 11 and 12 for admission of contact materials and for their rejection when spent.

Vapors resulting from upiiow treatments may be passed from the treater through line 19; containing control valve 20, and either passed directly, if sufficiently fractionated, to a condenser through line 23, containing control valve 24, and line 30, containing control valve 31, or if further fractionation appears advantageous or desirable they may be diverted through line 25, containing treater to prevent gas lock. ,The liquid accumu-' lations comprising those already described and the reflexes from fractionator 2'7 entering the accumulator from line 49, containing control valve 50, may be withdrawn therefrom through a line 51, containing control valve 52, and pumped by a pump 53 through a line 54, containing control valve 55, to any suitable point of disposal.

Vapors from fractionator' 27 may pass through line 28, containing control valve 29, and thus by way of line 30. containing control valve 31, to condenser 32 which serves the purpose of liquefying gasoline fractions and cooling'fixed gases, the mixture passing through line 33, containing control valve 34, to receiver 35. From this point the fixed gases may be withdrawn through line 36, containing control valve 37, at a rate consistent with the maintenance of suitable back pressure upon preceding portions of the equipment and the treated gasoline constituting the end product of the process may be Withdrawn to storage or other mild final treatment through line 38, containing control valve 39. To assist in controlling the boiling point range of the vapors from the fractionator, a suitable portion of the end product liquids may be returned to the top of the fractionator, those portions being led to recirculating pump 42 through line 40, containing control valve 41, and discharged therefrom through line 43, containing control valve 44.

I have found that the use of contact materials as described produces improved results in the treatment of hydrocarbon vapors to reduce gumforming constituents and sulfur compounds. It willbe evident that owing to the wide range in composition of the contact mass that it may be proportioned to give treatments of a more distinctly polymerizing character or of a more pronounced 'desulfurizing action. Thus, in general when polymerization is the main object as may occur when treating cracked vapors produced from paraifinic charging stocks of low sulfur content, the masses may contain relatively larger proportions of electro-positive metals, such as zinc and tin, whose chlorides have known polymerizing value. When a desulfurizing treatment is necessary, the proportion of electro-negative metal such as copper, silver, etcetera, may be somewhat increased. To account for the desulfurizing tendency of the contact masses thus employed in the presence of hydrochloric acid, it may be presumed that while the sulfur in organic combination has greater affinity for the electronegative metal and that corresponding sulfides are formed as intermediate products, these are decomposed due to the joint action of hydrochloric acid and the chloride of'the electro-positive metal, to liberate hydrogen sulfide. While this theory may not be entirely adequate to explain the complex reactions that are probably involved, the observations are definite to the effect that greater desulfurization is accomplished when using contact masses of the character described than when using compounds of electropositive or electro-negative metals alone.

In regard to the polymerizing effects observed, these may be accounted for either on the basis of the presence of chlorides of electro-positive metals such as zinc, tin, iron, etcetera, these chlorides having known polymerizing value, or upon the action of hydrochloric acid per se in contact with electro-negative metals such as copper orsilver, the latter functioning more in a catalytic sense.

As an example'of the value of the preconditioning of the contact masses which constitutes the chief feature of the present invention a case involving the use of brass turnings in a copper lined treating tower may be considered. When such a contact mass is used without preliminary treatment of hydrochloric acid it may be necessary to pass the hydrocarbon vapors mixed with hydrochloric acid over the mass for several hours before the maximum treating effect is observed, indicated by improvement in color and reduction in gum and sulfur content. By preliminarily treating the brass turnings'by percolating warm concentrated hydrochloric acid through them, the effect of the contact mass when the mixture of hydrocarbon vapors and hydrochloric acid is passed over them is immediately evident, the treating effect attaining its maximum possible under theconditions of treatment in a very short time. Thus, it is shown that the preliminary treatment increases the overall efficiency of the process by increasing the time during which the mass is available for treatment.

The preceding specification and data upon the results obtainable by the use of the improved treating process which it covers are sufflcient to enable one skilled in the art to appreciate its value, but both specification and the example are given for illustrative purposes only and are not to be considered in the light of imposing undue limitations upon the scope of the invention.

I claim as my invention:

1. In processes of the character wherein hydrocarbon oil is refined to remove color, gumforming and sulphur-containing components by subjecting the some while in heated condition to the action of hydrochloric acid while in contact with a metallic catalyst, the improvement which comprises preconditioning and activating said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to contact with the hydrocarbon oil.

2. In processes of the character wherein hydrocarbon oil is refined to remove color, gumforming and sulphur-containing components by subjecting the same while in heated condition to the action of hydrochloric acid while in contact with a metallic catalyst comprising zinc, the improvement which comprises, preconditioning and activating said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to contact with the hydrocarbon oil.

3. In processes of the character wherein hydrocarbon oil is refined to remove color, gum forming and sulphur-containing components by subjecting the same while in heated condition to the action of hydrochloric acid while in contact with a metallic catalyst comprising copper,

the improvement which comprises preconditioning and activating said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to contact with the hydrocarbon oil.

4. In processes of the character wherein hydrocarbon oil is refined to remove color, gum forming and sulphur-containing components by subjecting the same while in heated condition to the action of hydrochloric acid while in contact with a metallic catalyst comprising a mixture of zinc and copper, the improvement which comprises preconditioning and activating the said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to the introduction of the hydrocarbon oil.

5. In processes of the character wherein hydrocarbon oil is refined to remove color, gum forming and sulphur-containing components by subjecting the same while in heated vaporous condition to the action of the hydrochloric acid while in contact with a metallic catalyst comprising an alloy of zinc and copper, the improvement which comprises preconditioning and activating the said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to the introduction of the hydrocarbon vapors.

6. In processes of the character wherein hydrocarbon oil is refined to remove color, gum forming and sulphur-containing components by subjecting the same while in heated vaporous condition to the action of hydrochloric acid while in contact with a metallic catalyst comprising brass, the improvement which comprises preconditioning and activating the said metallic catalyst by subjecting the same to the action of hydrochloric acid prior to the introduction of the hydrocarbon vapors.

ROLAND B. DAY. 

